Tris(phosphono-lower alkylidene) amine oxides



United States Patent 3,474,133 TRIS(PHOSPHON0-LOWER ALKYLIDENE) AMINEOXIDES Marvin M. Crutchfield and Riyad R. Irani, St. Louis, Mo.,assignors to Monsanto Company, St. Louis, Mo., a corporation of DelawareNo Drawing. Original application Sept. 3, 1964, Ser. No. 394,350, nowPatent No. 3,429,914, dated Feb. 25, 1969. Divided and this applicationJune 6, 1968, Ser.

Int. 'Cl. 'C07f 9/38 U.S. Cl. 260-502.5 4 Claims ABSTRACT OF THEDISCLOSURE The present invention relates to and provides a tris(phosphono lower alkylidene) amine oxide from the group of acids havingthe formula 0 X 0 on ILM wherein X and Y are each from the grouphydrogen and lower alkyl. The alkali metal salts of the above-describedacids are also within the scope of this invention.

This application is a division of application Ser. No. 394,350, filedSept. 3, 1964 and now U.S. Patent 3,429,914.

This invention relates to organo-phosphono-arnine oxides and processesfor preparing the same.

An object of this invention is to provide new and usefulorgano-phosphono-amine oxide compounds containing at least one group permolecule.

A further object of this invention is to provide new and useful acidsand salts of organo-phosphono-amine oxide compounds containing at leastone wherein: X and Y are each selected from the group consisting ofhydrogen and lower alkyl (1-6 carbon atoms) and R and R are eachselected from the group consisting of alkyl, aryl, alkaryl, aralkyl,alicyclic, hydroxy-substituted derivatives of the foregoing,

3,474,133 Patented Oct. 21, 1969 and in R2 wherein: m is an integer from1 to 10, A when present is oxygen, and R and R does not contain over 6nitrogen atoms; and salts thereof selected from the group consisting ofalkali metals, alkaline earth metals, aluminum, ammonium and amines.

When the symbols R and R represent groups containing carbon chains, suchas alkyl groups or groups containing alkyl moieties, i.e., aralkylgroups and the like, such carbon chains may be of a straight chainstructure or a branched chain structure. Additionally, the carbon chainsshould preferably contain less than about 20 carbon atoms. For thesymbols R and R when representing alicyclio groups such are preferably 5and 6 membered mono-cyclic .alicyclic groups. When the symbols R and Rrepresent aryl groups and groups containing aryl moieties, i.e., alkarylgroups and the like, such groups are preferably mono-cyclic. Althoughthe carbon atoms of the alkyl, alicyclic, aryl, alkaryl, aralkyl groupsmay contain many hydroxy substituents, for example, at least one hydroxysubstituent per carbon atom in the group, it is preferred that suchgroups contain less than 1 hydroxy substituent per carbon atom in thegroup and more preferred for groups containing many carbon atoms, i.e.,about 4 carbon atoms or more, less than about 3 hydroxy substituents pergroup. For most end use applications the compounds of the instantinvention should preferably contain not more than about 25 carbon atomsassociated with R and R and there are few, if any, end uses in which theforegoing groups contain more than a total of 50 carbon atoms.

These compounds can be characterized quite generally as having at leastone linkages in their molecules and are generically described in thespecification by the general term organo-phosphonoamine oxides.

In general, the organo-phosphono-amine oxides can be prepared by theprocess of oxidizing organo-phosphonoamines with a suitable oxidizingagent. Suitable oxidizing agents are, in general, any oxidizing agentcontaining an OO linkage (peroxide compound) and having an oxidizingaction. In particular, suitable oxidizing agents include hydrogenperoxide, substituted peroxides and addition compounds of hydrogenperoxide, such as the peroxide of sodium and the super oxide ofpotassium, urea percompounds, perborates, persulfates and the peracidssuch as persulfuric acid, per acetic acid, peroxy monophosphoric acidand the like as well as their water soluble salt compounds such assodium, potassium, ammonium and organic amine salts, with hydrogenperoxide being particularly preferred. In general, the oxidation processcan be carried out in an aqueous medium, i.e., an aqueous solvent orsuspension, as well as in organic solvents such as alcohols, benzene andthe like. Although excessive temperature conditions should be avoideddue to the possible degradation of either the organo-phosphono-amine ororgano-phosphono-amine oxide and/or the dangerous tendency of theoxidizing agent to decompose rapidly, ordinary or elevated temperaturesi.e., from about 0 to 100 C. and even higher in some cases, can be usedwith temperatures from about 20 to C. being preferred. Concentrations ofthe oxidizing agent in the reaction medium can vary considerably,however, it is preferred to use concentrations above about by weight ofthe reaction medium with concentrations from about to 50% by weightbeing particularly preferred. It should be noted that with compoundscontaining more than 1 nitrogen atom it is possible by varying thereaction conditions to either oxidize substantially all of the nitrogenatoms or only one nitrogen atom to the amine oxide form.

The salts of the organo-phosphono-amine oxides can be prepared byneutralization of the acids with a stoichiometric amount of a base orsalt that contains essentially the desired cation or by conversion ofthe organo-phosphone-amine to a salt form prior to its oxidation to theamine oxide. Bases or salts of volatile acids such as those containingan alkali metal, alkaline earth metal, aluminium, ammonia and amines areespecially suited. For example, to make a sodium salt, one of the freeacids of the organo-phosphono-amine oxides can be neutralized with astoichiometric amount of a base containing the sodium cation, such asNaOH, Na CO and the like.

For the foregoing methods of preparation reaction con ditions such astemperature, pH and time for reaction can be varied with the optimumconditions for the reactions readily ascertained by those skilled in theart. It has been found that a convenient method for determiningfavorable conditions in individual cases is provided by the H and Pnuclear magnetic resonance (n.m.r.) signals which can be obtained from asmall sample i.e., about 0.5 ml., of the reaction mixture. The formationof the semi-polar bond between nitrogen and oxygen as the reactionproceeds produces a change in the local magnetic environments of thehydrogen atoms on the carbon atoms adjacent to the N O group as well asof the phosphorus atoms. As a result the n.m.r. signals which areobserved for these atoms in the starting amine slowly disappear as thereaction proceeds, while simultaneously new and different signals areobserved to appear for these atoms in the amine oxide reaction product.Observation of these signals can also serve to warn of extremeconditions of excessive time and/or temperature which can lead toadditional undesired oxidation or even complete destruction of theproduct. Additionally, for starting materials which are appreciablywater-soluble, such as tris(dihydrogen phosphonomethyl)amine, N[CH PO Hthe reaction is conveniently carried out in aqueous solution with theformation of water-soluble products which can be isolated by theevaporation of solvent and excess peroxide either under vacuum, or atatmospheric pressure. For starting materials which are not readilysoluble in water, such as decyl, bis(dihydrogen phosphonomethyl)amine,

use of an organic solvent or conversion of the phosphono acid group orgroups to a soluble salt form is preferred to increase the aqueoussolubility of the amine prior to reaction with the peroxide. Forstarting materials which are sparingly soluble in water or peroxidesolution and which form amine oxides which are appreciably more watersoluble, such as, tetrakis(dihydrogen phosphonomethyl)ethylene diamine,

the reaction can be preferably carried out by making an aqueous slurryof the starting material in peroxide solution with the slurry graduallyturning to a homogeneous solution as the reaction proceeds. Reference tothe specific examples presented hereinafter may be of further aid inorder to assist in teaching the methods of their preparation.

The organo-phosphono-amines useful as starting materials to prepare thecompounds of instant invention can be prepared by the reaction of anitrogeneous material (ammonia, primary amines or secondary amines), acompound containing a carbonyl group (aldehyde or ketone) andorthophosphorous acid. Generally, by heating the mixture above about 50C. at a relatively low pH, preferably about 2 or below, the extent ofthe reaction is usually completed in a few hours. Another method is thehydrolysis of the esters of the organo-phosphono-amines withconcentrated HCl or HBr. Generally, by refluxing the ester and acid atreflux temperature for a period of a few hours is all that is requiredfor the hydrolysis.

In general, the organo-phosphone-amine oxides of the present inventionhave utility in practically all fields of organic chemistry whereintheir acidic or salt and/or amine oxide properties can be utilized.

In particular, the compounds of the instant invention can find utilityin such fields as sequestering or chelating agents, water-treatingagents, stabilizers for peroxy compounds, soap anti-oxidants, additivesin liquid soap, detergents and shampoos, agents for use in scouring woolcloth and cotton kier boiling, metal cleaning compositions, rubber andplastic compositions and polymerization processes, bottle washingcompositions, dairy cleaning compositions, agents for use in pulp andpaper processing, corrosion inhibitors, feed and vegetation supplementsherbicides, insecticides, metal treating compositions, electroplating,detergent builders or additives, lime soap dispersants, surfactants,film formers in hair sprays and soluble packages, dispersants for clays,drilling muds, paper pulps, inorganic and organic pigments, and cementslurries, bactericide potentiators, hair modifiers in shamposs,fertilizers, food and beverage acidulants, leavening agents, cheeseemulsifiers, modifying agents in evaporated and condensed milk, flameretardants in paints and plastics, oil additives, gasoline additives,dentrifice compositions and the like.

In particular, the acids and water-soluble salts of the tris(phosphonolower alkylidene)amine oxides were found to exhibit the property ofbeing effective sequestering agents for metal ions in alkaline mediums.For example, the penta sodium salt of tris(dihydrogenphosphonomethyl)amine oxide was found to sequester Ca ions in alkalinemedia in over a mole per mole basis (Ca++ per sequestering agent). Theacid compounds are of the following formula:

wherein X and Y are each selected from the group consisting of hydrogenand lower alkyl (1-4 carbon atoms). Although any water-soluble salt canbe used, the preferred salts are the sodium salts and in particular thepenta sodium salts although other alkali metal salts, such as potassium,lithium and the like, as well as mixtures of the alkali metal salts maybe used.

In particular, the acids and water-soluble salts of the higher alkylbis(phosphono lower alkylidene)amine oxides were found to exhibit theproperty of being effective surfactants and lime soap dispersants. Theacid compounds are of the following formula:

wherein X and Y are each selected from the group consisting of hydrogenand lower alkyl (1-4 carbon atoms) and R is an alkyl group containingfrom 4 to 20 carbon atoms. Although any water-soluble salt can be used,the preferred salts are the sodium salts and in particular the trisodiumsalts although other alkali metal salts, such as potassium, lithium andthe like, as well as mixtures of the alkali metal salts may be used.

The following examples are presented to illustrate the invention, withparts and percentages by weight being used in the examples unlessotherwise indicated.

EXAMPLE 1 In a suitable reaction vessel about grams of tris(dihydrogenphosphono methyl)amine is added to about 169 ml. of 30% H 0 and thereaction mixture is stirred for about 12 hours at about 35 C. Thereaction product is dried at about 25 C. under a stream of dry air. Theproduct, after being washed with methanol and air dried, yields about119 grams of tris(dihydrogenphosphono methyl)amine oxide, O=N(CH BO HElemental analysis yields the following results:

Analysis.Calculated (percent): C, 11.44; H, 3.84; P, 29.50; N, 4.45; O,50.78. Found (percent): C, 11.39; H, 3.81; P, 29.39; N, 4.34; O, 51.07.

The equivalent weight of this product, by titration, is found to beabout 317 which compares favorably "with the calculated value of about315. The P and H n.m.r. spectra are consistent with the formation of anbond. The acid titration curve indicates that the acid dissociationconstants of the product diifer from those of the starting amine.

The sodium salt, bis (disodium phosphonomethyl) (monosodium hydrogenphosphonomethyl)amine oxide, ON(CH PO NaH) (CH PO Na is prepared bydissolving about 31.5 grams of the free acid obtained as in this examplein about 50 grams of H 0 and neutralizing by the addition of about 40.0grams of 50% NaOH. The aqueous solution is evaporated to dryness undervacuum below 50 C.

The monocalcium salt, calcium tetrahydrogen tri(phosphonomethyl) amineoxide,

ON (CH PO Ca) (CH P O H 2 is prepared by dissolving about 31.5 grams ofthe free acid obtained as in this example in about 100 grams of waterand precipitating by the slow addition of about 22.2 grams of 50% CaClsolution. The calcium salt is filtered off, washed and air dried.

EXAMPLE 2 In a suitable reaction vessel about 22 grams of methyl, bis(dihydrogen phosphonomethyl amine,

is added to about 34 grams of 30% H 0 and stirred for about 1 to 2 hoursat about 90 C. Analysis of the P n.m.r. spectrum of the product, aviscous syrup, after being dried by evaporation under a stream of dryair at 25 C., indicates methyl, bis(dihydrogen phosphonomethyl)amineoxide, CH N(O) (CH PO H The potassium salt, methyl, (dipotassiumphosphonomethyl) (monopotassium hydrogen phosphonomethyl) amine oxide,CH N(O) (CH PO KH) (CH PO K) is prepared 'by dissolving about 21.9 gramsof the free acid in about 33.6 grams of 50% KOH solution and evaporatingthe aqueous solution to dryness at about 50 C.. under vacuum.

EXAMPLE 3 In a suitable reaction vessel about 31.3 grams of tris-(dihydrogen phosphono ethylidene)amine is added to about 22.3 grams of30% H 0 and the reaction mixture is stirred for about 20 hours at about40 C. Evaporation at about 25 C. under a stream of dry air yields theamine oxide, tris(dihydrogen phosphono ethylidene) amine oxide, N(O)(CHCHPO H The diammonium salt, bis(monoammonium hydrogen phosphonoethylidene) (dihydrogen phosphono ethylidene) amine oxide, ON(CHCI-IPONH H) (CH CHPO H is prepared by dissolving about grams of the freeacid in about 20 grams of water, followed by the addition ofconcentrated NH solution, until the pH of the mixture is about 3.5. Theammonium salt is then obtained by evaporation of the solvent undervacuum at about 25 C.

EXAMPLE 4 In a suitable reaction vessel about 13.9 grams of dimethyl,(dihydrogen phosphonomethyl)amine is added 6 to about 22.3 grams of 30%H 0 and the reaction mixture is stirred for about 48 hours at about 60C. H and P n.m.r. spectra of the reaction mixture show reaction to formthe amine oxide, dimethyl (dihydrogen phosphonomethyl)amine oxide, (CHN(O)CH PO(CH) Addition of excess of a saturated solution of aluminumnitrate, Al(NO precipitates as a gelatinous solid 3)2 2 2( )la EXAMPLE 5In a suitable reaction vessel about 29.3 grams of dodecyl,methyl(dihydrogen phosphono methyl)amine is neutralized with about 60grams of 10% NaOH and about 22.3 grams of 30% H 0 is added. The reactionmixture is stirred for about 40 hours at about 50 C. Excess hydrogenperoxide is destroyed at about 25 C. by the addition of a trace ofcatalase enzyme and the reaction mixture poured into cold excessconcentrated HCl. The free acid, dodecyl, methyl (dihydrogenphosphonomethyl)amine oxide,

precipitates and is separated by filtration. The solid product is washedwith acetone and air dried.

A portion of the above acid is converted to the ammonium salt bydissolving in excess concentrated NH solution and evaporating to drynessat 0 C. under vacuum. The product is dodecyl, methyl(monoammoniumhydrogen phosphonomethyl)amine oxide.

EXAMPLE 6 Into a suitable reaction vessel about grams of decyl,bis(dihydrogen phosphonomethyl)amine, about 47.5 grams of 50% NaOH andabout 227 grams of H 0 are charged and heated to dissolve the acid. Tothis reaction mixture, about 39.5 grams of 50% H 0 are added and thisreaction mixture is heated to about 60 C. for about 10 hours. Aftercooling the solution to about 25 C., about 500 mg. of catalase is addedto destroy the excess peroxide by standing for about 24 hours. A portionof this solution is added to excess concentrated HCl with a precipitateforming which is filtered, washed with acetone, and air dried. Analysisof the P n.m.r. spectra of the product indicates decyl, bis(dihydrogenphosphonomethyl)amine oxide, C10H21N(O) (CH2PO3H2)2.

A portion of the acid product solution obtained as in this example isneutralized with 50% NaOH solution to a pH of about 10.5 and afterdrying by evaporation for several days at about 25 C. yields the sodiumsalt, decyl, (disodium phosphonomethyl) (monosodium hydrogenphosphonomethyl)amine oxide,

C H N(O) (CH PO NaH) (CH PO Na EXAMPLE 7 Into a suitable reaction vesselabout 40.1 grams of tetradecyl, bis(dihydrogen phosphonomethyl)amine,about 24 grams of 50% NaOH and about 100 grams of H 0 are charged andheated to dissolve the acid. To this reaction mixture, about 19.4 gramsof 50% H 0 are added and this reaction mixture is heated to about 60 C.for about 24 hours. After cooling the solution to about 25 C., about 500mg. of catalase enzyme is added to destroy the excess peroxide. Aportion of this solution is added to excess concentrated HCl with aprecipitate forming which is filtered, Washed with acetone and airdried. The precipitated product is tetradecyl, bis(dihydrogenphosphonomethyl)amine oxide,

C H N(O) [CH PO(OH) EXAMPLE 8 In a suitable reaction vessel about 43.6grams of tetrakis (dihydrogen phosphonomethyl)athylene diamine isslurried in about 68 grams of 30% H 0 and stirred for about 24 hours atabout 35 C. The reaction product, after being evaporated in air toremove excess solvent yields about 46 grams of solid material. Analysisof the P n.m.r. spectra of the product indicates tetrakis (dihydrogenphosphonomethyl)ethylene diamine, N,N'-dioxide,

0 (H2O3PCH2)2I ICHzCH2IE( CH2P 03112):

A hexasodium salt is prepared by dissolving about 23 grams of the freeacid in about 60 grams of 20% NaOH solution, followed by evaporation todryness under vacuum at about 50 C.

A diamine salt is prepared by adding about 23 grams of the free acid toabout 36.5 grams of a 20% solution of a n-butyl amine in water. Onevaporation to dryness under vacuum is obtained as a sticky solid.

EXAMPLE 9 In a suitable reaction vessel about 24.9 grams of ethanolbis(dihydrogen phosphonomethyl)amine is added to about 22.3 grams of 30%H 0 and stirred for about 24 hours at about 60 C. Evaporation at about25 C. under vacuum yields the amine oxide, ethanol bis(dihydrogenphosphonomethyl)amine oxide A mono-calcium salt is prepared bydissolving about 13 grams of the free acid in about 26 grams of H 0,followed by the slow addition of about 27.5 grams of 20% CaCl solution.Solid (HOC H )N(O) [CH PO(OH)2] [CH PO Ca] precipitates, is filteredoif, washed with water and dried.

EXAMPLE 10 In a suitable reaction vessel about 35.1 grams of ethanol,tetradecyl(dihydrogen phosphonomethyl)amine is neutralized with about12.0 grams of 50% NaOH solution plus sulficient water to solubilize.About 22.3 grams of 30% H 0 is added and the reaction mixture is stirredfor about 48 hours at about 60 C. Excess H 0 is destroyed and thereaction mixture poured into cold concentrated HCl. The free acid,ethanol, tetradecyl, (dihydrogen phosphonomethyl)amine oxide,

precipitates and is removed by filtration. The product is washed withwater and air dried.

About 18.8 grams of the free acid is dissolved in about 56 grams of aKOH solution which is subsequently evaporated to dryness under vacuum toyield the mono potassium salt (HOC H (C 4H29)N(O)CH PO(OH)K.

EXAMPLE 11 In a suitable reaction vessel about 45.0 grams of tetrakis(dihydrogen phosphonomethyl)trimethylene diamine is slurried in about 68ml. of 30% H 0 and stirred for about 24 hours at about 35 C. Thereaction product, after being air dried at about 25 C. to remove excesssolvent yields about 47 grams of solid tetrakis (dihydrogenphosphonomethyl)trirnethylene diamine, N,N'-dioxide,

0 O r r (HgOaP CH3)Nz-CHz-CHz-CHz-N( CHzP 0 11 3 EXAMPLE 12 In asuitable reaction vessel about 57.3 grams of pentakis (dihydrogenphosphonomethyl)diethylene triamine is slurried in about 68 grams of 30%H 0 and stirred for about 48 hours at 35 C. The reaction product, afterevaporation of excess solvent, yields pentakis (dihydrogenphosphonomethyl)diethylene triamine, N,N,N"-trioxide.

0 o o 2O3PCHghI iCHzCHzlE(CHgP 03H.) CHZCHZIIKCHZP 0.112

EXAMPLE 13 In a suitable reaction vessel about 46 grams bis(dihydrogenphosphonomethyl), bis (dihydrogen phosphono isopropylidene)ethylenediamine is slurried in about 68 grams of 30% H 0 and stirred for about48 hours at about 35 C. The reaction product is then evaporated todryness at about 25 C. under vacuum to yield solid bis(dihydrogenphosphonomethyl), bis(dihydrogen isopropylidene)ethylene diamine, N,N,dioxide,

0 O (HzOaFCHzhlECHzCHzIITK CH3)2C P OaHz]:

EXAMPLE 14 In a suitable reaction vessel about 34.6 grams of nhexyl, bis(dihydrogen phosphono isopropylidene)arnine is dissolved in about gramsof 10% NaOH and about 22.3 grams of 30% H 0 is added thereto. Thesolution is heated at about 60 C. for about 12 hours. Excess sol vent isremoved by vacuum evaporation to yield the salt,

EXAMPLE 15 In a suitable reaction vessel about 28.1 grams of phenylbis(dihydrogen phosphonomethyl)amine is slurried with about 22.3 gramsof 30% H 0 and heated at about 50 C. for about 24 hours with efficientstirring. Excess water and peroxide are removed by vacuum evaporation toyield phenyl bis(dihydrogen phosphonomethyl)amine oxide,

In a suitable reaction vessel about 28.7 grams of cyclohexyl,bis(dihydrogen phosphonomethyl)amine is slurried with about 34 grams of30% H 0 and heated to about 50 C. for about 24 hours with eflicientstirring. Vacuum evaporation of excess water and H 0 yield cyclohexyl,bis(dihydrogen phosphonomethyl)amine oxide,

2 ca u l z a zlz Other compounds of the instant invention which can beprepared according to the procedure as illustrated by the foregoingexamples include the following:

(1) N (2 hydroxyethyl, tris(dihydrogen phosphono methyl)ethylene diamineN,N-dioxide.

(2) Tetrakis (dihydrogen phosphono methyDhexamethylene diamine,N,N-dioxide.

(3) Tetrakis(dihydrogen phosphono methyDheptamethylene diamineN,N'-dioxide.

(4) Tetrakis(dihydrogen phosphono methyDdOdecamethylene diamine,N,N-dioxide.

vention according to the procedures as illustrated by the foregoingexamples include the inorganic alkali metal, alkaline earth metal andaluminum salts, oxides and hydroxides, such as, NaCl, NaNO Na O, Na CONaHCO KOH, K 0, KCl, K CO KNO LiOH, LiCl, LiNO Li CO CsOH, CaCl, CsNO CsCO CaCI CaO, CaCO MgCL MgCO BaCO BaCI Ba(OH) SrCO SrCl Sr(OH) Al(OH) A1Al(NO and amines, particularly low molecular weight amines, i.e., havinga molecular weight below about 300, and more particularly the alkylamines, alkylene amines and alkanol amines containing not more than 2amines groups, such as, ethyl amine, diethylamine, propyl amine,propylene diamine, hexyl amine, 2-ethyl hexyl amine, N-butyl ethanolamine, triethanol amine and the like.

What is claimed is:

1. A tris(phosphono lower alkylidene)amine oxide selected from the groupconsisting of acids having the forsalts thereof.

2. A tris (phosphono lower alkylidene)amine oxide having the formula 0 x0 OH 3( 3 3 t wherein X and Y are each selected from the groupconsisting of hydrogen and lower alkyl.

3. An alkali metal salt compound of a tris(phosphono loweralkylidene)amine oxide having the formula wherein X and Y are eachselected from the group consisting of hydrogen and lower alkyl and Z isselected from the group consisting of hydrogen and alkali metals with atleast one group represented by Z being alkali metal.

4. Tris(dihydr0gen phosphono methyl) amine oxide.

References Cited UNITED STATES PATENTS OTHER REFERENCES Petrov et al.:Chem. Abstracts, vol. 54 (1960), col. 260.

BERNARD HELFIN, Primary Examiner I. E. EVANS, Assistant Examiner m3UNITED STATES PATENT OFFICE- CERTIFICATE OF CORRECTION Patent No. 3, 733 Dated October 21, 196

Inventofla) Marvin M. Crutchfield & Riyad R. Irani It is certified thaterror appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

Column 5, line 50, end of formula reading "(CH2PO3K)2" should read (CHPO K Column 6, line 5, last part of formula reading "(CH) should read(OH); Column 6, line 21, formula reading "(C H (CH )N(O)CH PO(OH shouldread ,C H )(CH )N(O)CH PO(0H) Column 6, line f beginning of formulareading "C H should read (314K339 Column 8, line 29, middle of forgulareading "PO Na should read P0 Na Column 9, line 19, after second Nformula reading "(CI-i PO(0H) should read (CH PO(OH) Column 10, line 24,beginning of formula reading "(CH should read (CH Column 10, line 58,after N formula reading "CH should read Column 10, line 63, the formulaw-ill gggegag-ag sholgn pelo wr O T c n m u mcn po n Hui- 311i?) N0; 319m AL) I'm-ms. m.

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